EP0139486B1 - Verfahren zur Herstellung von Zucker-Ketalen - Google Patents

Verfahren zur Herstellung von Zucker-Ketalen Download PDF

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Publication number
EP0139486B1
EP0139486B1 EP84306499A EP84306499A EP0139486B1 EP 0139486 B1 EP0139486 B1 EP 0139486B1 EP 84306499 A EP84306499 A EP 84306499A EP 84306499 A EP84306499 A EP 84306499A EP 0139486 B1 EP0139486 B1 EP 0139486B1
Authority
EP
European Patent Office
Prior art keywords
reaction
sugar
solvent
dried
added
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP84306499A
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English (en)
French (fr)
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EP0139486A2 (de
EP0139486A3 (en
Inventor
Koichi Matsumura
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Takeda Pharmaceutical Co Ltd
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Takeda Chemical Industries Ltd
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Publication date
Application filed by Takeda Chemical Industries Ltd filed Critical Takeda Chemical Industries Ltd
Publication of EP0139486A2 publication Critical patent/EP0139486A2/de
Publication of EP0139486A3 publication Critical patent/EP0139486A3/en
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Publication of EP0139486B1 publication Critical patent/EP0139486B1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H9/00—Compounds containing a hetero ring sharing at least two hetero atoms with a saccharide radical
    • C07H9/02—Compounds containing a hetero ring sharing at least two hetero atoms with a saccharide radical the hetero ring containing only oxygen as ring hetero atoms
    • C07H9/04—Cyclic acetals

Definitions

  • This invention relates to a process for producing sugar ketals.
  • the present invention provides a novel process for producing sugar ketals which are valuable derivatives in the chemistry of sugars.
  • the dehydration-condensation reaction of sugars with ketones is known as the ketal formation reaction, and a variety of procedures have been known so far.
  • acid catalysts such as mineral acids typified by sulfuric acid, hydrogen chloride, hydrogen bromide, phosphoric acid and perchloric acid, organic acids exemplified by acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid and acidic ion exchange resins, or Lewis acids exemplified by anhydrous aluminum chloride, tin tetrachloride, boron trifluoride, anhydrous zinc chloride and ferric chloride.
  • this ketal formation reaction involves a dehydration condensation reaction, it is common in almost all cases to use these acid catalysts in large quantities so that they may act as a dehydrating agent.
  • dehydrating agents which do not inhibit the reaction, such as phosphorus pentoxide, calcium chloride, anhydrous sodium sulfate, anhydrous copper sulfate, pyrosulfates, metaphosphoric acid esters, alum and molecular sieves.
  • the conventional techniques require the utilization of a large amount of acid catalysts or dehydrating agents; this results in a complicated post-treatment of reaction products in the step of isolating the objective compound, and also allows used dehydrating agents and huge amounts of salts by- produced in the neutralization step to turn into industrial wastes.
  • These techniques as an industrial production process may be considered to involve a seriously controversial reaction, when judging from the viewpoints of post-treatment problems and saving of natural resources.
  • side reactions such as self-condensation of ketones are ready to take place, because the catalysts to be employed in every case are strong acids.
  • EP-A-0,076,118 discloses that the ketal formation sugars can be catalysed by Lewis acids exemplified by anhydrous aluminium chloride, tin tetrachloride, boron fluoride, anhydrous zinc- chloride and ferric chloride.
  • the present inventor after extensive investigation in order to overcome these defects of the conventional processes, discovered the entirely new finding that the reaction of sugar and ketone in the presence of antimony pentachloride or antimony pentafluoride can produce sugar ketals in improved yields, and the finding was followed by further research, which has culminated in the present invention.
  • the present invention is directed toward a process for producing a sugar ketal, which comprises reacting a sugar with a ketone in the presence of antimony pentachloride or antimony pentafluoride.
  • the sugars which can be used in the present invention are not specifically limited, and include for example tetroses such as erythrose, threose, and erythrulose; pentoses such as arabinose, xylose, ribose, lyxose, ribulose and xylulose; hexoses such as glucose, galactose, talose, idose, gulose, mannose, altrose, fructose, sorbose, tagatose and psicose; sugar alcohols corresponding to sugars mentioned above such as erythritol, ribitol, arabitol, mannitol, sorbitol, dul- citol and innositol; and deoxy-sugars such as rhamnose, fucose and z-deoxyglucose.
  • tetroses such as erythrose, threose, and erythr
  • ketones which are useful in the present invention are not specifically restricted, but specific examples thereof include an alkyl ketone having a carbon number of 3 to 7 such as acetone, methyl ethyl ketone, diethyl ketone, di-n-propyl ketone and di-i-propyl ketone; and a cyclic ketone having a carbon number of 5 to 7 such as cyclopentanone, cyclohexanone and cyclohep- tanone.
  • alkyl ketone having a carbon number of 3 to 7 such as acetone, methyl ethyl ketone, diethyl ketone, di-n-propyl ketone and di-i-propyl ketone
  • a cyclic ketone having a carbon number of 5 to 7 such as cyclopentanone, cyclohexanone and cyclohep- tanone.
  • ketones to be used varies depending upon the structure of the objective compound, but such ketones are normally used at 2 to 10 times the theoretical amount in number of moles, though they are preferably employed, for example, at not less than 1 mole per mole of a sugar, not less than 2 moles and not less than 3 moles per mole of a sugar in cases in which the objective compound is a monoketal, diketal and triketal, respectively. And, these ketones may be used as a reactant- solvent, whereby they may be employed in large excess, unless they exert any adverse effect on the reaction.
  • Antimony pentachloride or antimony pentafluoride which are usable in the present invention may be either in the form of anhydride or hydrate.
  • the amount of antimony pentachloride or antimony pentafluoride to be used is not less than 0.01 weight %, preferably in the range of catalytic amount (0.03 weight %) to 10 weight %, more preferably in the range of 0.05 weight % to 5 weight %, all relative to the sugar.
  • antimony pentachloride and antimony pentafluoride may be employed in combination.
  • reaction solvent use can be made of various types of solvents, provided they do not interfere with the reaction.
  • nitromethane nitroethane, nitrobenzene, dichloromethane, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, ethyl bromide, pentane, cyclopentane, hexane, cyclohexane, heptane, benzene, toluene and xylene
  • the above-mentioned ketones can be used both as reactant and solvent; the reaction can also be carried out in a mixed solvent consisting of not less than two kinds of these solvents.
  • a small amount of water may be added at the time of the initiation of reaction.
  • the present reaction is an equilibrium reaction, and because the removal of the water produced in the reaction generally improves the yields, the reaction may be carried out while eliminating the water from the reaction system by a known procedure.
  • a known procedure in such a case, there may be mentioned distillative removal of water or use of drying agents.
  • the technique utilizing azeotropy of solvent and water is generally employed; the water may be separated and removed from the liquid obtained by cooling the vapors produced by azeotropic distillation, whereby the remaining solvent may be returned to a reaction vessel, or the azeotropic vapors may be removed out of the reaction system, followed by a new addition of an equal amount of the dried solvent to the reaction system.
  • azeotropic vapors may be dried with drying agents represented by anhydrous calcium sulfate, molecular sieves, alumina, etc. and subsequently returned to a reaction vessel.
  • the reaction temperature is normally in the range of 0°C to 150°C, preferably in the range of 20°C to 100°C.
  • the reaction may be conducted under reduced pressure.
  • the reaction time varies with the types of sugars and ketones, the amount of catalyst and reaction conditions, and is normally in the range of 30 minutes to 10 hours preferably in the range of 1 hour to 8 hours.
  • the reaction solvent may be distilled off as such, or after the reaction product is adjusted to the weakly alkaline pH (pH ca. 7 to 9) by the addition of a small amount of alkali (e.g., sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, ammonia and pyridine) or an aqueous solution of said alkali.
  • alkali e.g., sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, ammonia and pyridine
  • the objective sugar ketal can be easily obtained from the resulting residue by known means, such as extraction, distillation, column chromatography or recrystallization.
  • the present invention provides an industrially favorable process for producing sugar ketals.
  • the process of the present invention owing to the use in small amounts of antimony pentachloride or antimony pentafluoride which have been so far unknown as a catalyst for the acetal and ketal formation reaction, offers the characteristic features that the reaction can be allowed to proceed fully, that post-treatment of the reaction product is accordingly rendered outstandingly easy, with the objective sugar ketal being obtained in improved yields, that production of industrial wastes as is the case with the conventional processes is eliminated, that the utilization of catalyst in a small amount can reduce extremely the formation of byproducts (e.g., ketone dimer), shorten the reaction time and decrease a used amount of solvent, and so forth.
  • byproducts e.g., ketone dimer
  • the molecular sieve 3A referred to in the Examples, is referred to under the sub-heading "Molecular Sieves" at pages 703-5 of "Reagents for Organic Synthesis" by L. F. Fieser and M. Fieser.
  • the sieves are listed in the 1981-1982 Aldrich Catalog Handbook of Fine Chemicals published by The Aldrich Chemical Co. of 940, West Saint Paul Avenue, Milwaukee, Wisconsin 53233, U.S.A. with the indications "4-to 8-mesh Fieser 1,703, Disp D". According to the above Fieser reference molecular sieve 3A corresponds to the formula

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Saccharide Compounds (AREA)

Claims (10)

1. Verfahren zur Herstellung eines Zucker-Ketals, umfassend die Umsetzung eines Zuckers mit einem Keton in Gegenwart von Antimonpentachlorid oder Antimonpentafluorid.
2. Verfahren nach Anspruch 1, worin der Zukker eine Tetrose, eine Pentose, eine Hexose oder ein Zuckeralkohol oder ein Desoxyzucker derselben ist.
3. Verfahren nach Anspruch 2, worin die Pentose Arabinose oder Xylose ist.
4. Verfahren nach Anspruch 2, worin die Hexose, Sorbose, Glucose, Mannose, Fructose oder Galactose ist.
5. Verfahren nach Anspruch 2, worin der Zukkeralkohol Erythrit oder Mannit ist.
6. Verfahren nach Anspruch 2, worin der Desoxyzucker Rhamnose ist.
7. Verfahren nach Anspruch 1, worin das Keton ein Alkylketon mit einer Kohlenstoff-Zahl von 3 bis 7 oder ein cyclisches Keton mit einer Kohlenstoff-Zahl von 5 bis 7 ist.
8. Verfahren nach Anspruch 7, worin das Alkylketon Aceton oder Diethylketon ist.
9. Verfahren nach Anspruch 7, worin das cyclische Keton Cyclohexanon oder Cyclopentanon ist.
10. Verfahren nach irgendeinem der Ansprüche 1 bis 9, worin das Antimonpentachlorid und Antimonpentafluorid gemeinsam verwendet werden.
EP84306499A 1983-09-27 1984-09-24 Verfahren zur Herstellung von Zucker-Ketalen Expired EP0139486B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP179872/83 1983-09-27
JP58179872A JPS6069092A (ja) 1983-09-27 1983-09-27 糖ケタ−ルの製造法

Publications (3)

Publication Number Publication Date
EP0139486A2 EP0139486A2 (de) 1985-05-02
EP0139486A3 EP0139486A3 (en) 1985-05-29
EP0139486B1 true EP0139486B1 (de) 1988-07-13

Family

ID=16073377

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84306499A Expired EP0139486B1 (de) 1983-09-27 1984-09-24 Verfahren zur Herstellung von Zucker-Ketalen

Country Status (7)

Country Link
US (1) US4659809A (de)
EP (1) EP0139486B1 (de)
JP (1) JPS6069092A (de)
KR (1) KR850002484A (de)
CA (1) CA1230330A (de)
DE (1) DE3472679D1 (de)
DK (1) DK455984A (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3505150A1 (de) * 1985-02-15 1986-08-21 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von zuckerketalen
USH708H (en) * 1986-04-17 1989-11-07 Method of producing diacetone sorbose
JPH01157976A (ja) * 1987-12-16 1989-06-21 Towa Kasei Kogyo Kk （４ｓ，５ｓ）−４，５−シクロヘキシリデンジオキシ−２−シクロペンテン−１−オンとその鏡像体及びそれらの合成中間体並びにそれらの製造方法
DE4303821A1 (de) * 1993-02-10 1994-08-11 Boehringer Ingelheim Kg Verfahren zur Herstellung von 1,2-5,6-Diaceton-D-glucose
EP0779289A4 (de) * 1994-08-29 1999-06-02 Kao Corp Synthetische schmieröle
CN100413875C (zh) * 2003-03-31 2008-08-27 联化科技股份有限公司 2－脱氧－n－苯基戊糖胺的生产方法
CN101085791B (zh) * 2006-06-06 2011-04-13 浙江新和成股份有限公司 一种2-脱氧-n-苯基戊糖胺的制备方法
JP5580191B2 (ja) * 2010-12-27 2014-08-27 花王株式会社 抗酸化剤

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3139443A (en) * 1961-02-13 1964-06-30 Iit Res Inst Method of making acetals and compositions resulting therefrom
US3607862A (en) * 1969-02-04 1971-09-21 Hoffmann La Roche Process for preparing carbohydrate ketals
DE2003067A1 (de) * 1969-02-04 1970-08-06 Hoffmann La Roche Verfahren zur Herstellung von Ketalzuckern
US3598804A (en) * 1969-02-04 1971-08-10 Hoffmann La Roche Preparation of ketals
CH560725A5 (de) * 1969-04-10 1975-04-15 Magyar Tudomanyos Akademia
US3622506A (en) * 1969-06-27 1971-11-23 Universal Oil Prod Co Regeneration of crystalline aluminosilicates
KR840001591A (ko) * 1981-09-29 1984-05-07 구라바야시 이꾸시로 당케탈류의 제조방법
JPS58167582A (ja) * 1982-03-29 1983-10-03 Takeda Chem Ind Ltd 糖ケタ−ルの製造法

Also Published As

Publication number Publication date
DK455984D0 (da) 1984-09-25
EP0139486A2 (de) 1985-05-02
DE3472679D1 (en) 1988-08-18
CA1230330A (en) 1987-12-15
US4659809A (en) 1987-04-21
JPS6069092A (ja) 1985-04-19
EP0139486A3 (en) 1985-05-29
KR850002484A (ko) 1985-05-13
DK455984A (da) 1985-03-28

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